Kinetic Resolution of Axially Chiral 2‐Amino‐1,1′‐Biaryls by Phase‐Transfer‐Catalyzed N‐Allylation

Abstract

Produktive Phase: Die selektive kinetische Racematspaltung der Titelverbindungen, die wichtige chirale Bausteine sind, wurde durch phasentransferkatalysierte N‐Allylierung erreicht. Die Synthesemethode wurde auf die hoch enantioselektive Desymmetrisierung einer Biarylverbindung angewendet.

Understanding the Reactivity and Selectivity of Fluxional Chiral DMAP‐Catalyzed Kinetic Resolutions of Axially Chiral Biaryls

“…The biological relevance of chiralalcohols hasdriven the development of many methods for their kinetic resolution (KR), which have been subjected to numerous experimental and theoretical studies. [1][2][3][4][5][6][7][8][9][10][11][12][13] Amonga vailables trategies for the KR of alcohols, chiral 4-dimethylaminopyridine (DMAP) catalyzed KRs are particularly appealingd ue to their operational simplicity,h igh turnover,a nd environmental friendliness. [14][15][16][17][18][19] Studying such reactions computationally not only enriches our understanding of thesep rocesses but also creates opportunities to improvetheir efficiency.…”

Fluxionally Chiral DMAP Catalysts: Kinetic Resolution of Axially Chiral Biaryl Compounds

“…The catalytic kinetic resolution of 2‐amino‐2′‐hydroxy‐1,1′‐binaphthyl (nobin) derivatives remains a challenging problem, and only limited examples have been reported 7c. 8 Among them, the reported chiral DMAP acylation showed only modest selectivity 8.…”

Highly Enantioselective Kinetic Resolution of Axially Chiral BINAM Derivatives Catalyzed by a Brønsted Acid

“…However, examples of catalytic kinetic resolution of axially chiral BINAM derivatives, to the best of our knowledge, have not been reported. Although during the preparation of this manuscript, an efficient method for the kinetic resolution of 2‐amino‐1,1′‐biaryl compounds by phase‐transfer‐catalyzed N ‐allylation was reported by Maruoka and co‐workers,10 only one BINAM derivative was utilized as the substrate with fairly good results. Therefore, it still remains a challenging undertaking for the catalytic kinetic resolution of these axially chiral compounds.…”